KR20160062059A - Systems and methods for solvent-free delivery of volatile compounds - Google Patents

Abstract

A system and method for solventless delivery of volatile compounds is provided wherein an energy source is used to release the volatile compound. The systems and methods provided herein provide for (1) a solvent (e.g., water) is not required; (2) immediate release of volatile compounds (e.g., 1-MCP can be released from HAIP within a few milliseconds or seconds instead of a few minutes or hours of conventional methods of using water); And / or (3) can immediately start and stop the delivery of the volatile compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a system and a method for solventless transfer of a volatile compound,

Previous experiments have shown that molecular complexes of volatile compounds (e.g., 1-methylcyclopropene (1-MCP) complexed with alpha-cyclodextrin, its powder is also known as a high active ingredient product (HAIP) When heated, there is a significant weight loss due to decomposition of volatile compounds. Since 1-MCP (a typical active volatile compound) is known to decompose when heated, it is assumed that 1-MCP is decomposed when its molecular complex is heated to a high temperature (e.g., ~ 200 ° C).

1-MCP is well known to be liberated from alpha-cyclodextrin / 1-MCP complexes under moisture. Currently, all commercial 1-MCP generators use water to produce 1-MCP to treat a variety of fruits and vegetables. However, existing methods have the disadvantage that the release of 1-MCP requires prolonged time (for example 1 hour) and is sensitive to the quality of the water used.

Thus, there remains a need for systems and methods for solventless delivery of volatile compounds including 1-MCP.

The present invention is based on the surprising result that heating molecular complexes of 1-MCP and alpha-cyclodextrin (e.g., HAIP) can produce pure 1-MCP without significant loss. A system and method for solventless delivery of volatile compounds is provided wherein a source is used to release volatile compounds. The systems and methods provided herein provide for (1) a solvent (e.g., water) is not required; (2) immediate release of volatile compounds (e.g., 1-MCP can be released from HAIP within a few milliseconds or seconds instead of a few minutes or hours of conventional methods of using water); And / or (3) can immediately start and stop the delivery of the volatile compound.

In one aspect, a solventless system for delivery of volatile compounds is provided. The system comprises: (a) a molecular complex of a volatile compound and a molecular encapsulating agent; (b) treatment compartment; And (c) an energy source.

In yet another aspect, a solventless system for delivery of volatile compounds is provided. The system comprises: (a) a molecular complex of a volatile compound and a molecular encapsulating agent; (b) treatment compartment; And (c) means of an energy source.

In one embodiment, the system further comprises an elastomer. In a further embodiment, the elastomer comprises ethylene vinyl acetate. Further suitable elastomers are described in U.S. Patent Nos. 2006/0233857 and 2012/0273586, the contents of which are incorporated herein by reference in their entirety.

In one embodiment, the cyclopropene has the formula:

Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; Wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.

In a further embodiment, R is C ₁ -C ₈ alkyl. In another embodiment, R is methyl.

In one embodiment, the cyclopropene has the formula:

Wherein R ¹ is selected from substituted or unsubstituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkenyl, C ₁ -C ₄ alkynyl, C ₁ -C ₄ cycloalkyl, cycloalkylalkyl, phenyl or naphthyl Group; R ² , R ³ and R ⁴ are hydrogen.

In a further embodiment, the cyclopropene is 1-methylcyclopropene (1-MCP).

In one embodiment, the cyclopropene is part of a cyclopropene molecular complex. In another embodiment, the cyclopropene molecular complex is an inclusion complex. In another embodiment, the cyclopropene molecular complex comprises a cyclopropene and a molecular encapsulating agent. In a further embodiment, the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, crown ethers, zeolites, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises a cyclodextrin. In another embodiment, the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

In one embodiment, the treatment compartment is selected from the group consisting of a thermal desorption tube, a glass bottle, a Tedlar bag, an aluminum cup, and combinations thereof. In another embodiment, the energy source comprises at least one of electrical energy, magnetic energy, electromagnetic energy, ultrasonic energy, acoustic energy and thermal energy. In another embodiment, the energy source comprises at least one energy characteristic of waveform, frequency, amplitude or duration. In a further embodiment, the energy source comprises ultraviolet (UV) radiation. In another embodiment, the energy source does not comprise UV radiation.

In one embodiment, the energy source is between 100 DEG C and 300 DEG C; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Lt; RTI ID = 0.0 > 200 C. < / RTI > In yet another embodiment, the means of the energy source is selected from the group consisting of 100 占 폚 to 300 占 폚; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Or about < RTI ID = 0.0 > 200 C. < / RTI > In another embodiment, the means of the energy source is performed in a closed environment. In a further embodiment, it includes a closed environment cryogenic room / facility, refrigerator, shipping container and combinations thereof. In a further embodiment, the enclosed environment is selected from the group consisting of a cryogenic storage room / facility, a refrigerator, a shipping container, and combinations thereof. In another embodiment, the means of the energy source is selected from the group consisting of -30 DEG C to 10 DEG C; -20 DEG C to 5 DEG C; -10 ° C to 0 ° C; Or at an ambient temperature of about 4 < 0 > C. In a further embodiment, the means of the energy source is carried out in a cryogenic storage or cryogenic storage facility.

In another embodiment, the energy source is provided by passing hot air. In another embodiment, the means of the energy source comprises passing hot air. In one embodiment, the hot air comprises an inert gas. In a further embodiment, the inert gas is helium. In another embodiment, the hot air is at a temperature of from 100 DEG C to 300 DEG C; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Or about 200 < 0 > C.

In another aspect, a method of delivering a volatile compound is provided. The method comprises: (a) providing a molecular complex of a volatile compound and a molecular encapsulating agent; (b) disposing a molecular complex into the treatment compartment; (c) applying the energy source to the treatment compartment, thereby releasing the volatile compound from the molecular complex.

In another aspect, a method of delivering a volatile compound is provided. The method comprises: (a) providing a molecular complex of a volatile compound and a molecular encapsulating agent; (b) disposing a molecular complex into the treatment compartment; (c) applying the means of the energy source to the treatment compartment, releasing the volatile compound from the molecular complex.

In one embodiment, the loss of volatile compounds is 40%; 30%; 20%; 10%; Or less than 5%. In another embodiment, the loss of volatile compounds is from 40% to 0.5%; 30% to 1%; 20% to 3%; Or 10% to 5%. In another embodiment, the system provided herein is used. The loss of volatile compounds is defined as the comparison between the amount of volatile compounds encapsulated and the amount of volatile compounds recovered after release.

In one embodiment, the cyclopropene has the formula:

Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; Wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy.

In a further embodiment, R is C ₁ -C ₈ alkyl. In another embodiment, R is methyl.

In one embodiment, the cyclopropene has the formula:

Wherein R ¹ is selected from substituted or unsubstituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkenyl, C ₁ -C ₄ alkynyl, C ₁ -C ₄ cycloalkyl, cycloalkylalkyl, phenyl or naphthyl Group; R ² , R ³ and R ⁴ are hydrogen.

In a further embodiment, the cyclopropene is 1-methylcyclopropene (1-MCP).

In one embodiment, the cyclopropene is part of a cyclopropene molecular complex. In another embodiment, the cyclopropene molecular complex is an inclusion complex. In another embodiment, the cyclopropene molecular complex comprises a cyclopropene and a molecular encapsulating agent. In a further embodiment, the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, crown ethers, zeolites, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises a cyclodextrin. In another embodiment, the molecular encapsulating agent is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

In one embodiment, the treatment compartment is selected from the group consisting of a thermal desorption tube, a glass bottle, a teddy bag, an aluminum cup, and combinations thereof. In another embodiment, the energy source comprises at least one of electrical energy, magnetic energy, electromagnetic energy, ultrasonic energy, acoustic energy and thermal energy. In another embodiment, the energy source comprises at least one energy characteristic of waveform, frequency, amplitude or duration. In a further embodiment, the energy source comprises UV radiation. In another embodiment, the energy source does not comprise UV radiation.

In one embodiment, the energy source is between 100 DEG C and 300 DEG C; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Lt; RTI ID = 0.0 > 200 C. < / RTI > In yet another embodiment, the means of the energy source is selected from the group consisting of 100 占 폚 to 300 占 폚; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Or about < RTI ID = 0.0 > 200 C. < / RTI > In another embodiment, the means of the energy source is performed in a closed environment. In a further embodiment, the enclosed environment includes a cryogenic storage room / facility, a refrigerator, a shipping container, and combinations thereof. In a further embodiment, the enclosed environment is selected from the group consisting of a cryogenic storage room / facility, a refrigerator, a shipping container, and combinations thereof. In another embodiment, the means of the energy source is selected from the group consisting of -30 DEG C to 10 DEG C; -20 DEG C to 5 DEG C; -10 ° C to 0 ° C; Or at an ambient temperature of about 4 < 0 > C. In a further embodiment, the means of the energy source is carried out in a cryogenic storage or cryogenic storage facility.

In another embodiment, the energy source is provided by passing hot air. In another embodiment, the means of the energy source comprises passing hot air. In one embodiment, the hot air comprises an inert gas. In a further embodiment, the inert gas is helium. In another embodiment, the hot air is at a temperature of from 100 DEG C to 300 DEG C; 150 DEG C to 250 DEG C; 180 DEG C to 220 DEG C; Or about 200 < 0 > C.

In another aspect, a method of delaying maturation for a plant or plant part is provided. In one embodiment, the method comprises treating a plant or plant part using the system provided herein. In another embodiment, the method comprises treating a plant or plant part using the methods provided herein.

In yet another aspect, an apparatus for solventless delivery of volatile compounds is provided. In one embodiment, the apparatus comprises the components disclosed in the systems provided herein. Additional suitable devices are described in U.S. Patent Nos. 7,540,286, 7,832,410, U.S. Patent Application 2006/0037998 and International Patent Application WO 2013/034453, the contents of which are incorporated herein by reference in their entirety.

1 shows an exemplary schematic view of a vaporizer as part of the system provided herein, wherein 101 denotes an air inlet, 102 denotes a fan, 103 denotes a heater, 104 denotes a sample holder, And 105 denotes an air outlet.
Figure 2 shows an exemplary schematic of a generator as part of the system provided herein wherein 201 represents a sample cup 202 represents a gas outlet 203 represents an upper end of aluminum 204 represents nitrogen (N ₂₎ represents the inlet port, 205 denotes a silicon gasket, 206 denotes a isolated, 207 denotes an aluminum block, 208 represents a heater.

The present invention relates to the production of 1-MCP gas by heating HAIP (1-MCP / alpha-cyclodextrin complex). The results of the present invention suggest that it is possible to quantitatively produce 1-MCP upon heating of alpha -cyclodextrin / 1-MCP complexes. In one embodiment, surprising data from thermogravimetric analysis-mass spectrometry (TGA-MS) suggest that heating HAIP to a temperature of about 200 ° C can produce pure 1-MCP. In another embodiment, a treatment protocol is provided that does not require water but can produce 1-MCP in a few milliseconds. In another embodiment, a delivery system and / or device is provided for producing 1-MCP by heating HAIP.

The results of the present invention are surprising because numerous studies have established that 1-MCP is degraded to other molecules at temperatures above 100 < 0 > C. (W. Schnivasan, R. Journal of the American Chemical Society, 1969, 91, 6250-6253; Hopf, H.; Wachholz, G .; Walsh, R. Chemische Berichte, 1985, 118, 3579-3587 ] Reference).

The cyclopropene used herein is any compound having the formula:

Wherein each R ¹ , R ² , R ³ and R ⁴ is independently selected from the group consisting of H and a chemical group of the formula:

- (L) _n -Z

In the above formula, n is an integer of 0 to 12. Each L is a divalent radical. Suitable L groups include, for example, radicals containing one or more atoms selected from H, B, C, N, O, P, S, Si or mixtures thereof. The atoms in L groups may be connected to each other by a single bond, a double bond, a triple bond, or a mixture thereof. Each L group may be linear, branched, cyclic or a combination thereof. In any one R group (i.e., any one of R ¹ , R ² , R ³ and R ⁴ ), the total number of heteroatoms (ie, not H and not C) is 0-6. Independently, in any one R group, the total number of non-hydrogen atoms is 50 or less. Each Z is a monovalent radical. Each Z is independently selected from the group consisting of hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanato, isothiocyanato, pentafluorothio, Group G wherein G is a 3 to 14 membered ring.

The R ¹ , R ² , R ³ and R ⁴ groups are independently selected from suitable groups. The R ¹ , R ² , R ³ and R ⁴ groups may be the same as each other, or any of them may be different from each other. Among the groups suitable for use as at least one of R ¹ , R ² , R ³ and R ⁴ , for example, an aliphatic group, an aliphatic-oxy group, an alkylphosphonato group, a cycloaliphatic group, a cycloalkylsulfonyl group , A cycloalkylamino group, a heterocyclic group, an aryl group, a heteroaryl group, a halogen, a silyl group, other groups, and mixtures and combinations thereof. The groups suitable for use as at least one of R ¹ , R ² , R ³ and R ⁴ may be substituted or unsubstituted. Independently, groups suitable for use as one or more of R ¹ , R ² , R ^3, and R ⁴ may be linked directly to the cyclopropene ring or may be linked to the cyclopropene ring via a spacer, for example, via a heteroatom- It can be connected to a pen ring.

Suitable R ¹ , R ² , R ³ and R ⁴ groups include, for example, aliphatic groups. Some suitable aliphatic groups include, but are not limited to, alkyl, alkenyl, and alkynyl groups. Suitable aliphatic groups may be linear, branched, cyclic or combinations thereof. Independently, suitable aliphatic groups may be substituted or unsubstituted.

As used herein, when one or more hydrogen atoms of a chemical group of interest are replaced by a substituent, the chemical group of interest is referred to as "substituted ". It is contemplated that such substituted groups may be prepared by any method including, but not limited to, preparing an unsubstituted form of the chemical group of interest, followed by performing the substitution. Suitable substituents include alkyl, alkenyl, acetylamino, alkoxy, alkoxyalkoxy, alkoxycarbonyl, alkoxyimino, carboxy, halo, haloalkoxy, hydroxy, alkylsulfonyl, alkylthio, trialkylsilyl, dialkylamino and combinations thereof But are not limited thereto. Additional suitable substituents which may be present, when present, either alone or in combination with another suitable substituent are the following:

- (L) _m -Z

Wherein m is from 0 to 8, and L and Z are defined herein. When more than one substituent is present in a single chemical group of interest, each substituent may replace a different hydrogen atom, or one substituent may be attached to another substituent so that it is eventually attached to the chemical group of interest, or May be a combination thereof.

Suitable R ¹ , R ² , R ³ and R ⁴ groups include, but are not limited to, substituted and unsubstituted aliphatic-oxy groups such as, for example, alkenoxy, alkoxy, alkynoxy and alkoxycarbonyloxy.

Also suitable among the R ¹ , R ² , R ³ and R ⁴ groups are, without limitation, alkylphosphonato, dialkylphosphonato, dialkylthiophosphonato, dialkylamino, alkylcarbonyl and di Substituted and unsubstituted alkylsulfonyl, substituted and unsubstituted arylsulfonyl, alkylaminosulfonyl, substituted and unsubstituted alkylphosphonato, substituted and unsubstituted alkylphosphonato, substituted and unsubstituted alkylamino, substituted and unsubstituted alkylsulfonyl , Substituted and unsubstituted alkylcarbonyl, and substituted and unsubstituted alkylaminosulfonyl.

Also suitable among the R ¹ , R ² , R ³ and R ⁴ groups are, without limitation, substituted and unsubstituted cycloalkylsulfonyl and cycloalkylamino groups such as, for example, dicycloalkylaminosulfonyl and dicycloalkyl Amino.

Also included among the suitable R ¹ , R ² , R ³ and R ⁴ groups are, but are not limited to, substituted and unsubstituted heterocyclyl groups (ie, aromatic or nonaromatic cyclic groups having at least one heteroatom in the ring) .

Also included within the suitable R ¹ , R ² , R ^3, and R ⁴ groups are, but are not limited to, substituted and unsubstituted heterocyclyl groups linked to the cyclopropene compound via an intervening oxy, amino, carbonyl or sulfonyl group Have; Examples of such R ¹ , R ² , R ³ and R ⁴ groups are heterocyclyloxy, heterocyclylcarbonyl, diheterocyclylamino and diheterocyclylamino sulfonyl.

Also among the suitable R ¹ , R ² , R ³ and R ⁴ groups are, without limitation, substituted and unsubstituted aryl groups. Suitable substituents include those described herein above. In some embodiments, at least one substituent is selected from the group consisting of alkenyl, alkyl, alkynyl, acetylamino, alkoxyalkoxy, alkoxy, alkoxycarbonyl, carbonyl, alkylcarbonyloxy, carboxy, arylamino, haloalkoxy, halo, At least one substituted aryl group that is at least one of the following: alkyl, alkenyl, alkynyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl,

Also suitable among the R ¹ , R ² , R ³ and R ⁴ groups are, without limitation, those linked to the cyclopropene compound via an intervening oxy group, an amino group, a carbonyl group, a sulfonyl group, a thioalkyl group or an aminosulfonyl group A substituted and unsubstituted heterocyclic group; Examples of such R ¹ , R ² , R ³ and R ⁴ groups are diheteroarylamino, heteroarylthioalkyl and diheteroarylaminosulfonyl.

Suitable R ¹ , R ² , R ³ and R ⁴ groups also include but are not limited to hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido, chlorato, , Isocyanato, isothiocyanato, isothiocyanato, pentafluorothio, acetoxy, carboethoxy, cyanato, nitrite, nitrite, perchlorate, allenyl, Wherein the substituent is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, There is an analog.

As used herein, the chemical group G is a 3- to 14-membered ring system. Suitable ring systems as chemical groups may be substituted or unsubstituted; These may be aromatic (including, for example, phenyl and naphthyl) or aliphatic (including unsaturated aliphatic, partially saturated aliphatic or saturated aliphatic); These may be carbocyclic or heterocyclic. Of the heterocyclic G groups, some suitable heteroatoms are, without limitation, nitrogen, sulfur, oxygen and combinations thereof. Suitable ring systems as chemical groups may be monocyclic, bicyclic, tricyclic, polycyclic, spiro or fused; Of the suitable cyclic, fused or bicyclic ring systems, the various rings within a single chemical group G may all be of the same type or may be of more than one type (for example, the aromatic rings may be fused with an aliphatic ring) .

In some embodiments, G is a cyclic system containing a saturated or unsaturated ternary ring, such as, but not limited to, a substituted or unsubstituted cyclopropane, cyclopropene, epoxide, or aziridine ring.

In some embodiments, G is a cyclic system containing a 4-membered heterocyclic ring; In some of these embodiments, the heterocyclic ring contains exactly one heteroatom. In some embodiments, G is a cyclic system containing a heterocyclic ring having 5 or more members; In some of these embodiments, the heterocyclic ring contains 1 to 4 heteroatoms. In some embodiments, the ring in G is unsubstituted; In another embodiment, the ring system contains 1 to 5 substituents; In some embodiments where G contains a substituent, each substituent may be independently selected from the substituents described above in this disclosure. Also suitable are embodiments wherein G is a carbocyclic ring system.

In some embodiments, each G is independently substituted or unsubstituted phenyl, pyridyl, cyclohexyl, cyclopentyl, cycloheptyl, pyrrolyl, furyl, thiophenyl, triazolyl, pyrazolyl, / RTI > or morpholinyl. Among these embodiments are, for example, embodiments wherein G is unsubstituted or substituted phenyl, cyclopentyl, cycloheptyl or cyclohexyl. In some embodiments, G is cyclopentyl, cycloheptyl, cyclohexyl, phenyl, or substituted phenyl. Embodiments in which G is substituted phenyl include, but are not limited to, embodiments wherein one, two, or three substituents are present. Some embodiments in which G is substituted phenyl include, but are not limited to, embodiments wherein the substituent is independently selected from methyl, methoxy and halo.

It is also contemplated that R < ³ > and R < ⁴ > may be combined into a single group, which may be attached to the 3 carbon atom of the cyclopropene ring by a double bond. Some of these compounds are described in U.S. Patent Publication No. 2005/0288189.

In some embodiments, at least one cyclopropene in which at least one of R ¹ , R ² , R ^3, and R ⁴ is hydrogen may be used. In some embodiments, R ¹ or R ² or both R ¹ and R ² can be hydrogen. In some embodiments, either R ³ or R ⁴ or both R ³ and R ⁴ can be hydrogen. In some embodiments, R ² , R ^3, and R ⁴ can be hydrogen.

In some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ may be a structure that does not have a double bond. Independently, in some embodiments, at least one of R ¹ , R ² , R ^3, and R ⁴ may be a structure that does not have a triple bond. In some embodiments, at least one of R ¹ , R ² , R ^3, and R ⁴ may be a structure that does not have a halogen atom substituent. In some embodiments, at least one of R ¹ , R ² , R ^3, and R ⁴ may be a structure free of substituents that are ions.

In some embodiments, one or more of R ¹ , R ² , R ^3, and R ⁴ can be hydrogen or (C ₁ -C ₁₀ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ can be hydrogen or (C ₁ -C ₈ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ can be hydrogen or (C ₁ -C ₄ ) alkyl. In some embodiments, each of R ¹ , R ² , R ^3, and R ⁴ can be hydrogen or methyl. In some embodiments, R ¹ can be (C ₁ -C ₄ ) alkyl, and each of R ² , R ^3, and R ⁴ can be hydrogen. In some embodiments, R ¹ may be methyl, and each of R ² , R ^3, and R ⁴ may be hydrogen and the cyclopropene is referred to herein as "1-methylcyclopropene" or "1-MCP"Lt; / RTI >

In some embodiments, from 1 atmosphere to 50 캜 or less; Or 25 DEG C or less; Or a cyclopropene having a boiling point of 15 DEG C or lower may be used. In some embodiments, at -1 atmospheric pressure to -100 C or higher; -50 ° C or higher; Or -25 DEG C or higher; Or a cyclopropene having a boiling point of 0 ° C or higher may be used.

Cyclopropene can be prepared by any method. Some suitable methods for the preparation of cyclopropenes include, but are not limited to, those disclosed in U.S. Pat. Nos. 5,518,988 and 6,017,849.

In some embodiments, the composition may comprise at least one molecular encapsulating agent for cyclopropene. In some embodiments, the at least one molecular encapsulating agent can encapsulate at least one cyclopropene or at least a portion of at least one cyclopropene. Complexes containing a cyclopropene molecule or a portion of a cyclopropene molecule encapsulated within the molecule of a molecular encapsulating agent are known herein as "cyclopropene molecular complex" or "cyclopropene compound complex ". In some embodiments, the cyclopropene molecular complex comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 32, 40, 50, 60, 70, 80 90% by weight (w / w).

In some embodiments, at least one cyclopropene molecular complex may be present as an inclusion complex. In such inclusion complexes, the molecular encapsulating agent forms a cavity, and a portion of the cyclopropene or cyclopropene is located within the cavity. In some embodiments of the inclusion complex, there may be no covalent bond between the cyclopropene and the molecular encapsulating agent. In some embodiments of the inclusion complex, whether or not there is any electrostatic attraction between one or more polar moieties in the cyclopropene and one or more polar moieties in the molecular encapsulating agent, between the cyclopropene and the molecular encapsulating agent There may be no ionic bond.

In some embodiments of the inclusion complex, the interior of the cavity of the molecular encapsulating agent may be substantially nonpolar or hydrophobic or both, and the cyclopropene (or a portion of the cyclopropene located within the cavity) may also be substantially nonpolar or hydrophobic Both can be. Although the present invention is not limited to any particular theory or mechanism, in such a non-polar cyclopropene molecular complex, the van der Waals forces or hydrophobic interactions, or both, may cause cyclopropene molecules or portions thereof to remain within the cavities of the molecular encapsulating agent .

Cyclopropene molecular complexes can be prepared by any means. In one preparation method, for example, such a complex can be prepared by contacting the cyclopropene with a solution or slurry of the molecular encapsulating agent, for example using the method disclosed in U.S. Patent No. 6,017,849, and isolating the complex. For example, in another method in which cyclopropene is encapsulated in a molecular encapsulating agent, the cyclopropene gas is bubbled through a solution of the molecular encapsulating agent in water, from which the complex is first precipitated, . ≪ / RTI > In some embodiments, complexes may be prepared through any of the above methods and stored after drying and drying in solid form, e.g., powder, for later addition to useful compositions.

The amount of molecular encapsulating agent can be characterized by the ratio of mol of molecular encapsulating agent to mol of cyclopropene. In some embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene is 0.1 or greater; 0.2 or more; 0.5 or more; Or 0.9 or more. In some embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene is 2 or less; Or 1.5 or less.

Suitable molecular encapsulating agents include, but are not limited to, organic and inorganic molecular encapsulating agents. Suitable organic molecular encapsulating agents include, but are not limited to, substituted cyclodextrins, unsubstituted cyclodextrins and crown ethers. Suitable inorganic molecular encapsulating agents include, but are not limited to, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable. In some embodiments, the encapsulating agent may be alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or mixtures thereof. In some embodiments, alpha-cyclodextrin can be used. In some embodiments, the encapsulating agent may vary depending on the structure of the cyclopropene or cyclopropene used. Mixtures of any cyclodextrin or cyclodextrin, cyclodextrin polymers, modified cyclodextrins, or mixtures thereof may also be used. Some cyclodextrins are available, for example, from Wacker Biochem Inc. of Adrian, Mich., Or Cerestar USA of Hammond, Indiana, as well as from other vendors.

Energy sources - Suitable primary energy sources that can be used include conduction, convection, and radiation. Conduction energy can be generated by electrical resistance (e.g., cartridge heater, formed resistance wire, ceramic heater, band heater, wire film heater and thin flexible heater). Convection heating can be achieved by flowing a heated gas or by flowing a heated liquid. Radiation energy sources include, for example, lasers, microwaves, and infrared radiation.

Embodiments include methods of treating plants with the systems and / or methods described herein. In some embodiments, treating the plant or plant part with the provided system and / or method inhibits the ethylene response in the plant or plant part. The term "plant" is commonly used to include plant-grown crops, potted plants, cut flowers, harvested fruits and vegetables, and corn plants as well as woody-stem plants. Examples of plants that can be treated with embodiments include, but are not limited to, those listed below.

In some embodiments, the plant or plant part can be treated with a cyclopropene at a level that inhibits the ethylene response in the plant or plant part. In some embodiments, the plant or plant part may be treated at a level below the phytotoxic level. The level of phytotoxicity may vary not only with the plant but also with the cultivar. Treatment can be performed on growing plants, or on plant parts harvested from growing plants. In carrying out the treatment on a growing plant, it is contemplated that the composition can be contacted with the whole plant or with one or more plant parts. Plant parts include any part of the plant, including, but not limited to, flowers, buds, flowering, seeds, turnings, roots, bulbs, fruits, vegetables, leaves and combinations thereof. In some embodiments, plants may be treated with the compositions described herein before or after harvesting of useful plant parts.

Suitable treatments may be performed on fields, gardens, buildings (e. G., Greenhouses), enclosed containers or plants or parts of plants in other locations. Suitable treatments may be carried out on the oak, one or more containers (e.g., pollen, jar or vase), clogged or raised beds, or plants planted elsewhere. In some embodiments, the treatment may be performed on the plant in a location other than the building. In some embodiments, the plant may be treated while growing in a container, such as a flowerpot, a flatbed, or a mobile bed. In another embodiment, the provided systems and methods are performed in a closed environment. In a further embodiment, the enclosed environment includes a cryogenic storage room, a refrigerator, a shipping container, or a combination thereof.

When properly used, the systems and methods described herein prevent numerous ethylene effects, many of which are disclosed in U.S. Patent Nos. 5,518,988 and 3,879,188, both of which are incorporated herein by reference in their entirety. Using the embodiments described herein, one or more of the plant ethylene reactions can be affected. The ethylene reaction can be initiated by an exogenous or endogenous ethylene source. The ethylene response may include the following: (i) the ripening and / or senescence of flowers, fruits and vegetables; (ii) the elimination of leaves, flowers and fruits; (iii) the extension of the life of ornamental plants such as potted plants, cut flowers, shrubs and dormant seedlings; iv) inhibition of growth in some plants such as pea plants; And (v) stimulation of plant growth in some plants, such as rice plants.

Vegetables that can be treated to inhibit senescence include leafy green vegetables such as lettuce (for example, Lactuca sativa ), spinach ( Spinacia oleracea ) and cabbage Brassica oleracea ); Various roots such as potatoes ( Solanum tuberosum ) and carrots ( Daucus carota ); Bulbs such as onion ( Allium sp.); Herbs such as basil ( Ocimum basilicum ), oregano ( Origanum vulgare ) and dill ( Anethum graveolens ); It is also possible to use soybeans such as soybean ( Glycine max ), lima beans ( Phaseolus limensis ), peas ( Lathyrus sp.), Corn ( Zea mays ), broccoli ( Brassica oleracea italica ), cauliflower ( Brassica oleracea botrytis ), and asparagus ( Asparagus officinalis ), but are limited thereto It does not.

Fruits which may be treated by the method of the present invention to inhibit ripening is tomatoes (Ricoh beaded cone S. Cullen Tomb (Lycopersicon esculentum)), apple (say loose FIG scalpel urticae (Malus domestica)), banana (Musa Sapienza Tomb (Musa sapientum ), pears ( Pyrus communis ), papaya ( Carica papaya ), mangoes ( Mangifera indica ), peaches ( Prunus persica ) ( Prunus persica nectarina ), orange ( Citrus sp.), Lemon ( Citrus limonia ), Prunus persica nectarina ( Prunus persica nectarina ), Prunus armeniaca ( Prunus armeniaca ) , Citrus aurantifolia ), grapefruit ( Citrus paradisi ), tangerine ( Citrus nobilis deliciosa ), kiwi (actinidiaquinensis Actinidia chinensis ), Melons such as cantaloupe ( C. cantalupensis ) and muskmelon ( C. melo ), pineapple ( Ananas comosus ), persimmon ( Diospyros ) Such as Diospyros sp.) And raspberry (e.g., Fragaria or Rubus ursinus ), blueberries ( Vaccinium sp.), Green beans Phaseolus vulgaris ), members of the genus Cucumis such as cucumber ( C. sativus ) and avocado ( Persea americana ).

Ornamental plants that can be treated by the method of the present invention to inhibit senescence and / or to prolong flower life and appearance (e.g., delayed wilting) include, but are not limited to, pollen tubers and cut flowers. The potted ornamental plants and cut flowers that can be treated are Rhododendron spp., Hydrangea macrophylla, Hibiscus rosa-sinensis ( Hibiscus rosa-sinensis ), Rhododendron spp. )), snapdragon (anti rinum species (Antirrhinum sp.)), poinsettia (yuporeubiah pool Kerry town (Euphorbia pulcherrima)), cactus (e.g., syulrum bereuge la Troon Catarina (Schlumbergera truncata)), begonia (Begonia species (Begonia ( Rosa sp.), Tulip ( Tulipa sp.), Narcissus sp. ( Narcissus sp.), Petunia ( Petunia hybrida ) , Carnations ( Dianthus caryophyllus ), lilies (e.g. Lilium sp.), Gladiolus ( Gladiolus sp.), Alstroemeria (alstroemeria, Alstroemeria brasiliensis ), anemone (e.g., (For example, Anemone blanda ), Aquilegia sp., Aralia chinesis , flower (for example, Astarolinia sp. Aster carolinianus , Bougainvillea sp., Camellia sp., Campanula sp., Celosia sp. )), cypress (on the Kama Faris species (Chamaecyparis sp.)), chrysanthemum (Creative Sante drought species (chrysanthemum sp.)), clematis (clematis species (clematis sp.)), cyclamen (cyclamen species (cyclamen orchids with Freisia (e.g., Freesia refracta ) and Orchidaceae, but are not limited thereto.

Plants that can be treated to inhibit the elimination of leaves, flowers and fruits include cotton ( Gossypium spp.), Apples, pears, cherries ( Prunus avium ), pecans ( Carva illinoensis ), grapes ( Vitis vinifera ), olives (e.g., Olea europaea ), coffee ( Coffea arabica ), kidney beans Including but not limited to dormant seedlings of a variety of fruit trees, including, but not limited to, apple seedlings (eg, Phaseolus vulgaris ) and rubber trees ( Ficus benjamina ) But are not limited thereto.

In addition, the shrubs that can be treated to inhibit the desorption of the leaves can be selected from the group consisting of pellets ( Ligustrum sp.), Potentia ( Photina sp.), Ilex sp.), Ferns with Polypodiaceae, Schefflera sp., Aglonema sp. ( Aglaonema sp.), Trees ( Cotoneaster sp.), Berberis sp. ( Berberis sp.), Myrica sp. ( Myrica sp.), Abalia sp. ( Abelia sp. ), Acacia ( Acacia sp.), And bromeliad with Bromeliaceae. ≪ RTI ID = 0.0 >

The phrase "plant" as used herein includes dicotyledonous plants and monocotyledonous plants. Examples of ssangjayeop plants, dicotyledonous plants, dicotyledonous plants or dicotyledonous flow tobacco, Arabidopsis (Arabidopsis), soybeans, tomatoes, papaya, canola, sunflower, cotton, alfalfa, potatoes, vines, Pigeon Blood, peas, Brassica (Brassica) Squash, broccoli, cabbage, carrots, cauliflower, celery, cabbage, cucumber, eggplant and lettuce, and the like. Monocotyledonous plants, monocotyledonous plants, monocotyledonous plants, or dyed cotton plants include corn, rice, wheat, sorghum, barley, rye, sorghum, orchids, bamboo, banana, pearls, lilies, oats, onions, millet and lime.

As used herein, the phrase "plant material" refers to a plant, leaf, stem, root, flower or flower part, fruit, pollen, egg cell, zygote, seed, stump, cell or tissue culture, Quot; In some embodiments, the plant material comprises cotyledons and leaves.

As used herein, the phrase "plant tissue" refers to a group of plant cells organized in structural and functional units. Any tissue of a plant in a plant system or culture may include any group of plant cells, for example, whole plants, plant organs, plant seeds, tissue cultures, and plant cells that are organized in structural and / or functional units.

An apparatus for solventless delivery of volatile compounds is also provided. In one embodiment, the apparatus comprises the components disclosed in the systems provided herein. Further suitable devices are disclosed in U.S. Patent No. 7,540,286 (suction device for aerosol particles), 7,832,410 (device for electronic cigarettes), U.S. Patent Application 2006/0037998 (thermal controlled actuator device), and international patent application WO 2013/034453 Tobacco device), the contents of which are incorporated by reference in their entirety. Modifications of these devices can be achieved based on the characteristics of the particular volatile compound to be delivered.

The present invention is further described in the following examples, which are provided for illustration and are not intended to limit the invention in any way.

Example

Example 1

10.38 g of the alpha -cyclodextrin / 1-MCP complex (supplied by AgroFresh, 1-MCP = 3.8%) was placed in a heat desorption tube and heated to 200 ° C At a flow rate of 9.8 mL / min. The final volume of the bag was 900 mL. The presence of 1-MCP was confirmed by mass spectrometry. The concentration of 1-MCP determined by gas chromatography was found to be 153 ppm. All 1-MCPs present in the starting sample were liberated (without degradation), with a white density of 197 ppm. Thus, 78% of the theoretical amount of 1-MCP was obtained in bags.

Example 2

0.57 mg of HAIP SF08016 (Agrofresh, 4.33% 1-MCP) was added into the 123 mL glass bottle and the bottle was closed (hermetically sealed) with a port for extraction of the analytical sample of gas (HAIP is an alpha -cyclodextrin And 1-MCP, wherein the 1-MCP concentration is between 3.5% and 4.6%). The bottle was then heated at different temperatures for 30 minutes and the concentration of 1-MCP in the bottle was determined by gas chromatography and is presented in Table 1.

Example 3

0.66 mg of HAIP SF08016 (Agrofresh, 4.33% 1-MCP) was added into the 123 mL glass bottle and the bottle was closed (hermetically sealed) with a port for withdrawal of the analytical gas sample. The bottle was then heated at 180 캜 for 30 minutes and the concentration of 1-MCP in the bottle was determined by gas chromatography. The concentration of 1-MCP was 121 ppm. The calculated value was 105 ppm.

Example 4

Using a commercial vaporizer (Extreme Q Vaporizer; see Figure 1), a series of experiments were performed using different sources and amounts of HAIP. For all of the experiments listed below, the heater was maintained at 230 DEG C and the fan set at the lowest setting (F-1) providing a flow rate of 954 milliliters per minute (mL / min). The outlet air was collected in a tether bag and the content was analyzed by gas chromatography to determine the 1-MCP concentration using isobutylene as an external standard (Al ₂ O ₃ refers to aluminum oxide).

The results in Table 2 show that by heating a complex between alpha -cyclodextrin and 1-MCP, pure 1-MCP can be produced in high yields, which can then be used to treat fruits and vegetables.

Example 5

A commercial vaporizer (extreme queue vaporizer; see Fig. 1) was modified to achieve a lower flow rate. A series of experiments were performed using different sources and volumes of HAIP.

For all the experiments listed below, the heater was maintained at a flow rate of 230 ° C and 254 mL / min. The outlet air was collected in a tether bag and the content was analyzed by gas chromatography to determine 1-MCP concentration using isobutylene as an external standard.

The results in Table 3 show that the yield of 1-MCP produced can be increased by lowering the flow rate from 954 mL / min to 254 mL / min and by adding iron to? -Cyclodextrin and 1-MCP .

Example 6

Using a newly designed generator (see FIG. 2) capable of heating tens of grams of HAIP, a series of experiments were performed using different amounts of HAIP and different block temperatures. The outlet air was collected in a large tether bag (40 liters (L)) and the content was analyzed by gas chromatography to determine 1-MCP concentration using isobutylene as an external standard.

% AI = percent active ingredient

¹ collection starts when the block temperature is 120 ° C

² N ₂ Flow rate is 1 liter per minute (L / min)

³ Run time is 90 minutes, with samples collected every 30 minutes

The data in Table 4 clearly show that heating a large amount of HAIP can produce 1-MCP in a high yield in less than 60 minutes. In all experiments, at least 71% of 1-MCP was liberated within 30 minutes. As the amount of HAIP increased, the formation of 2-butyne was observed, albeit to a very small extent (? 0.4%).

Example 7

To understand the heat flow from the heater block to the HAIP in a newly designed generator capable of heating dozens of HAIPs (see FIG. 2), a series of experiments were performed using different amounts of HAIP and different block temperatures. The temperature of the bulk powder was measured throughout the heating process.

Since the alpha-cyclodextrin has low thermal conductivity (0.0681 watts per meter Kelvin at 20 DEG C (w / mK) and 0.0841 w / mK at 150 DEG C) There was a sudden temperature drop in the powder. Under the block temperature setting at 200 占 폚, the temperature of the bulk powder (after 30 minutes) dropped from 140.5 占 폚 for 2 g sample (WJZ6546) to 105.9 占 폚 for 30 g sample (WJZ6552). In the 2 g experiment (WJZ6546), no 2-butyne was observed. Thus increasing the rate of 1-MCP production by increasing the heat transfer efficiency will reduce and possibly eliminate the formation of 2-butene.

In some embodiments, the invention may be further modified within the spirit and scope of the present disclosure. Accordingly, this application is intended to cover any variations, uses, or adaptations of the invention using its general principles. In addition, this application is intended to cover such derivative form from the present disclosure, as long as it is within the knowledge or practice of the art to which the invention belongs and which falls within the limits of the appended claims.

Claims (42)

(a) a molecular complex of a volatile compound and a molecular encapsulating agent;
(b) treatment compartment; And
(c) means of energy sources
And a solventless system for the delivery of volatile compounds. The system of claim 1, further comprising an elastomer. 3. The system of claim 2, wherein the elastomer comprises ethylene vinyl acetate. The system of claim 1, wherein the volatile compound comprises cyclopropene. 5. The system of claim 4, wherein the cyclopropene has the formula:

Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; Wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy. The method of claim 5, wherein, R is C ₁ -C ₈ alkyl system. 6. The system of claim 5, wherein R is methyl. 5. The system of claim 4, wherein the cyclopropene has the formula:

Wherein R ¹ is selected from substituted or unsubstituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkenyl, C ₁ -C ₄ alkynyl, C ₁ -C ₄ cycloalkyl, cycloalkylalkyl, phenyl or naphthyl Group; R ² , R ³ and R ⁴ are hydrogen. 5. The system of claim 4, wherein the cyclopropene is 1-methylcyclopropene (1-MCP). The system of claim 1, wherein the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, crown ethers, zeolites, and combinations thereof. The system of claim 1, wherein the molecular encapsulating agent comprises cyclodextrin. 12. The system of claim 11, wherein the cyclodextrin is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and combinations thereof. 2. The system of claim 1, wherein the processing compartment is selected from the group consisting of a thermal desorption tube, a glass bottle, a Tedlar bag, an aluminum cup, and combinations thereof. The system of claim 1, wherein the energy source comprises at least one of electrical energy, magnetic energy, electromagnetic energy, ultrasonic energy, acoustic energy, and thermal energy. 2. The system of claim 1, wherein the energy source comprises at least one energy characteristic of waveform, frequency, amplitude or duration. The system of claim 1, wherein the means of the energy source comprises heating to a temperature between 100 캜 and 300 캜. The system of claim 1, wherein the means of the energy source comprises heating to a temperature of from 150 캜 to 250 캜. 2. The system of claim 1, wherein the means of the energy source is performed in an enclosed environment. The system according to claim 1, wherein the means of the energy source is performed in an environment at a temperature of -30 캜 to 10 캜. The system according to claim 1, wherein the means of the energy source is performed in a cryogenic storage room or a cryogenic storage facility. (a) providing a molecular complex of a volatile compound and a molecular encapsulating agent;
(b) disposing a molecular complex into the treatment compartment;
(c) applying the means of the energy source to the treatment compartment, releasing the volatile compound from the molecular complex
≪ / RTI > 22. The method of claim 21 wherein the loss of volatile compounds is less than 20%. 22. The method of claim 21 using the system of claim 1. 22. The method of claim 21, wherein the volatile compound comprises cyclopropene. 25. The method of claim 24, wherein the cyclopropene has the formula:

Wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or naphthyl group; Wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy. 26. The method of claim 25, wherein R is C ₁ -C ₈ alkyl. 26. The method of claim 25, wherein R is methyl. 25. The method of claim 24, wherein the cyclopropene has the formula:

Wherein R ¹ is selected from substituted or unsubstituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkenyl, C ₁ -C ₄ alkynyl, C ₁ -C ₄ cycloalkyl, cycloalkylalkyl, phenyl or naphthyl Group; R ² , R ³ and R ⁴ are hydrogen. 26. The method of claim 24, wherein the cyclopropene is 1-methylcyclopropene (1-MCP). 22. The method of claim 21, wherein the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, crown ethers, zeolites, and combinations thereof. 22. The method of claim 21, wherein the molecular encapsulating agent comprises cyclodextrin. 32. The method of claim 31, wherein the cyclodextrin is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and combinations thereof. 22. The method of claim 21, wherein the processing compartment is selected from the group consisting of a thermal desorption tube, a glass bottle, a teddy bag, an aluminum cup, and combinations thereof. 22. The method of claim 21, wherein the energy source comprises at least one of electrical energy, magnetic energy, electromagnetic energy, ultrasonic energy, acoustic energy, and thermal energy. 22. The method of claim 21, wherein the energy source comprises at least one energy characteristic of waveform, frequency, amplitude or duration. 22. The method of claim 21, wherein the means of the energy source comprises heating to a temperature between 100 [deg.] C and 300 [deg.] C. 22. The method of claim 21, wherein the means of the energy source comprises heating to a temperature of from 150 DEG C to 250 DEG C. 22. The method of claim 21, wherein the means of the energy source is performed in a closed environment. 22. The method of claim 21, wherein the means of the energy source is performed in an environment at a temperature of -30 占 to 10 占 폚. 22. The method of claim 21 wherein the means of energy source is performed in a cryogenic storage room or cryogenic storage facility. A method for delaying maturation of a plant or a plant part, comprising treating the plant or plant part using the system of claim 1. 21. A method of delaying maturation of a plant or plant part, comprising treating the plant or plant part using the method of claim 21.

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